Heterojunction of (P, S) co-doped g-C3N4 and 2D TiO2 for improved carbamazepine and acetaminophen photocatalytic degradation

Abstract

Novel photocatalysts of phosphorus and sulfur co-doped graphitic carbon nitride incorporated in 2D TiO2 structure were successfully fabricated and applied for solar-driven degradation of emerging pollutants from the group of pharmaceuticals not susceptible to biodegradation. The hybrid photocatalysts with different loadings of (P, S)-doped g-C3N4 were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), UV–vis diffuse reflectance spectroscopy (DR/UV–vis), photoluminescence (PL) spectroscopy, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and transmission electron microscopy (TEM). The optimum (P, S)-doped g-C3N4/TiO2 (5 %) composite revealed improved photocatalytic activity towards the degradation of carbamazepine and acetaminophen. For CBZ, about 100 % degradation was achieved in less than 30 min of photodegradation, whereas for ACT, the complete removal was observed in 60 min of irradiation under simulated solar light. The multi-anion doped g-C3N4/2D TiO2 composite demonstrated an excellent synergy towards the degradation of CBZ and ACT with a synergy index of 1.35 and 1.62. Moreover, the mineralization efficiency measured as TOC removal was 76 % and 40 % for CBZ and ACT, respectively. The reactive oxygen species responsible for the degradation of selected pharmaceuticals are superoxide (O2–) and hydroxyl radicals (HO), and the kinetics of reactions proved to fit the first-order kinetics with a rate constant of 0.21 min−1 for CBZ degradation and 0.074 min−1 for ACT degradation. Our results suggest that (P, S)-doped g-C3N4/ 2D TiO2 heterostructure is a Z-scheme heterojunction, which can effectively separate photogenerated charge carriers. The emissions and decay times analyzed for single components and the optimal (P, S)-doped g-C3N4/ 2D TiO2 (5 %) composite confirmed interfacial charge transfer between TiO2 nanosheets and (P, S)-g-C3N4 and more effective separation of electron-hole pairs. Identification of carbamazepine and acetaminophen intermediates was performed using LC-MS analysis in combination with additional DFT calculations of the possible by-products formation. Regarding reusability, the photocatalytic activity of (P, S)-doped g-C3N4/ 2D TiO2 (5 %) was stable after subsequent cycles of carbamazepine and acetaminophen degradation.